Detergent compositions



June 29, 1937.

W. T. REDDlsH DETERGENT COMPOSITIONS Filed Sept. 2l, 1935l Patented June 29, 1937 DETERGENT COMPO SITIONS Warren T. Reddish, Cincinnati, Ohio, assigner to- Emery Industries, Inc., Cincinnati, Ohio, a corporation 0f Ohio Application September 21, 1933, SerialNo. 690,390

9 Claims.

This invention relates to a new detergent adapted for a multitude of processes such as home laundry use, powerlaundry use, degumming silk, scouring wool, or washing textiles of any nature at any time during the progress of their fabrication and finishing.

The invention can be best explained and understood when presented as an improvement over the subject matter of the British Patent No. 19,- 759, 1912, granted to Grigori Petroff, chemist, of Kuskowo, Russia. This patent refers to and must be `read in the light of its companion Patent No. 19,676 of 1912. The patent in question is entitled-An improved process of manufacturing detergents, detergent solutions, or emulsions. The disclosure ofthis patent is admirably summarized in the -i'lrst two claims, which read as follows:

1. A process for manufacturing a detergent which consists in employing the sulphonic acids extracted by means of alcohol or acetone or like solvents from sulphonated mineral oil hydrocarbons according to the process of Specification No. 19,676 of l1912l as the raw material for producing the detergent.

2. A process according to claim 1, for manufacturing a detergent which consists in treating the sulphonic acids either in a pure state or in admixture with flats, fatty oils, or fatty acids with caustic or carbonated alkalies or ammonia to obtainsI neutral, acid, or alkaline detergent mixture as desired.

, The speclcation, as well as 'the claims, abounds in the use of thedisjunctive and from this it may be inferred that Petroff had gone only so far as to ascertain Vthat his sulphonates were an appropriate raw material to be used as a soap, but that he had not made any determination of how the-sulphonates should be used.I The most that -Petroff claimed for his sulphonates is as follows:

In regard to its detergent powers, it is Iin no way inferior to good brands of soap made fronr 'However, though more than twenty years has elapsed since Petroffs work and disclosure, Petroifs novel raw material has never been'used either as soap or as an ingredient of soap. This raw material'has however been sold to the soap I 0 makers all over the world in tremendous quantities andhas been used by them in the making of soap as a substitute for the well-known Twitchell `reagent for the purpose of splitting fatty glycerides into fatty acid and glycerine. These circumstances conclusively establish the fact thateither Petroif was mistaken in his notion or hope that his new raw material was an appropriate ingradient for soap, or that the utilizationof his raw material as a soap ingredient was entirely beyond the skill of, the soap makers all over the world.

The present invention comprises the selection of ingredients for a detergent including Petroffs raw material and the proportioning of them to v provide a detergent far superior to those known in the past. More specifically, the detergent of this invention comprises alkali, fatty acids, and Petroffs mineral oil'sulphonics, or mahogany sulphonates, as they are known in this country at the present time. are conventional ones in almost all soap factories, and while all of them have been used as detergents or suggested for use as detergents still their specic functional relationships have neverbeen understood. On this account they have never been used in combination in practice and in view of the liberal use of the disjunctive in the Petroi disclosure, it cannot besaid that they have even been suggested in combination. 'I'his functional relationship of alkali, vfatty acid soap and mahogany sulphonates is so complex that it is only susceptible to explanation by diagram.

The accompanying drawing is a diagram disclosing how alkali, fatty acid soap and mahogany sulphonates, when used conjointly as a detergent,

produce a new and superior detergent result by virtue of the fact that each ingredient in combination with each other ingredient provides a function not provided by any ingredient alone.

' Any one of a number of different alkalies may be employed, such as caustic soda, soda ash, bicarbonate of soda, sodium metasilicate orv trisodium phosphate.

' The term alkali throughout the remainder of the specification and claims, vis used to include these materials and their chemical equivalents.

While all of these materials Instead of the 'sodium compounds of the type listed, the potassium compounds may be employed wherever. warranted as a matter 'of cost'. Now, one ofthe distinguishingcharacteristics of this invention is that alkali ing or treating in much greater quantities and at much higher concentrations than accepted standard practice. Of course, the quantityof alkali used in standard practice varies in different in"- dustries according to the nature of the specific problem and even varies among the different plants in a given industry. However, the alkalinity incorporated in this new detergent subis used for textile wash-` stan'tially exceeds previous practice for each use. One reason that the greater strength of alkali can be used without injury to the fabric is that the mahogany sulphonates employed herein seem to act as inhibitors in relation to the alkali and tend to'preserve the tensile strength of the fabric during the Washingprocess.

-In contrast to the British Petroif patent, which 'specifies that the sulphonate may be, acid, alkali or neutral, the present detergent is characterized by the presence of a very substantial and ponderable quantity of free alkali or potential alkali of y the nature disclosed. For instance, silk is easily injured by alkali and the quantity of alkali used for degumming silk is therefore substantially less than that employed for most of the washing processes. However, even for degumming silk the detergent of this invention comprises at least 5% by weight of a very strong alkali, such as caustic soda. It is therefore to be noted that the detergent of this invention, even at its lower limit of alkalinity, carries a percentage of free alkali which distinguishes it from that lesser degree of alkalinity which is substantially equivalent in operation to neutral or acid solution. In other words, Petro specifies that his acid, neutral or alkaline soaps and soap solutions are functionally equivalent and specifies that his starting material, sulphonic acids, optionally mixed with fatty acids. may be neutralized, under-neutralized or over-neutralized without affecting the detergent properties of the resulting soap.

'I'his invention onthe contrary is characterized by the presence of anywhere from one-third to twenty times the quantity of alkali'necessary to neutralize the mahogany sulphonic and fatty acid content of the admixture. This detergent is not functionally equivalent to an acid or neutral detergent or to an over-neutralized detergent, but on the contrary its detergent action may be saidto be dominated by the activity of the large quantity of free or potential alkali.

'I 'he fatty acid soap employed in this detergent may be of animal or vegetable origin and of any titre, the soap from fatty acids having a titre as low as ten having been found entirely satisfactory.

Red oil soap is entirely suitable for use in this detergent, though soaps from high titre fats, either alone or in combination with red oil soap, may be used.

One of the essential ingredients of the detergent of this invention is mahogany sulphonates. These bodies are produced in-the refining of petroleum or fractions thereof, such as lubricating stock,

' into medicinal white oil or the light colored technical oils. In this general process the petroleum is treated with fuxning sulphuric acid or sulphur trioxide, after which the sludge settles out. Next, the oill is treated with an alkali and an aqueous alcohol solution which extracts the mahogany sulphonates, leaving the white oil technical oil as aremainder.

Mahogany sulphonates are recovered from the aqueous alcoholic solution by evaporation. This general process has frequently been referred to in thepatentliterature as the Petroli-Humphrey process for the reason that it is practiced under Petroff Patent No. 1,087,888 and Humphrey Patent No. 1,286,179. f

. There are other variations of this general proc.- ess, though all of them produce sulphonic bodies which commercially are called mahogany sulphonates. Though these bodies are usually available in the form of the sodium salt of mahogany or light colored v,

mahogany sulphonates and 90 to 40% fatty acid soap, be followed. These limits were selectedI arbitrarily, and while not highly critical, are provided for the purpose of instructing the skilled in the art as to the general optimum blending ratio.

As shown in the accompanying drawing, the idea of this invention is to attack the soil on the fabrics or the sericin on raw silk or the wool grease on raw wool or the dressings used on textiles for lubrication or preservation in the course of their manufacture, with a powerful alkali.

The strong free alkali in solution attacks the saponiflable dirt and as it is used up by saponication, the fatty acid soap hydrolyzes and supplies' additional alkali (if necessary). The amount of alkali used likewise increases the detergency of the fatty acid soap-mahogany sulphonate mixture. Mahogany sulphonates do not hydrolyze. The fatty acid soap performs another function in conjunction with the mahogany sulphonates. Together they form a body which, in aqueous solution, has more power of suspending and emulsifying dirt, grease, wax and soil in general than does either one of them alone. Mahogany sulphonates from American petroleums do not in general form water soluble calcium and magnesium salts. However, these sulphonates in combination with fatty acid soap do possess the property of solubilizing calcium .and magnesium fatty acid soaps or mahogany sulphonates which may be formed as the vresult of hardness in the water employed for the washing process. 'I'his is of very great advantage and it has not been known before that the mixture of mahogany sulphonates and fatty acid soap would emulsify or susp'end the calcium or magnesium soaps.

The mahogany sulphonates and alkali in combination effect the removal of foreign matter from the textile or fibre being washed without injury to the fibre. The mahogany` sulphonates are themselves powerful emulsifying agents even for mineral oil. The combination of mahogany sulphonatesand of fattyv acid soap, suspends all types of dirt admirably.

The mahogany sulphonates accelerate lthe wetting out action of the detergent solution and also depress the interfacial tension between the alkaline solution and all oily, greasy or waxy a soil or foreign matter on the fabric. Moreover, as before stated, the mahogany sulphonates seem to alter the speed with which the alkali attacks the soil or foreign matter as compared with the speed 'with which the alkali attacks the textile fibre itself. This action is herein termed an inhibiting action arid is a very great advantage, especially in regard to silk or wool, both of which are sensitive to alkalies.

It is therefore to be observed that the use of this detergent for purposes of the type specified provides a very rapid cleansing operation which saves usually one-half of the time normally consumed. In power laundry work the total amount of water used is reduced substantially in half.

The clothes are washed much cleaner than is usual, do not tend to\become gray on repeated washings, and do not becomespecked with traces 2,085,471 vof insoluble calcium and magnesiumv salts when thereis hardness in the water. Moreover, the tensile strength ofthe fabric being cleansed does not seem to suffer to the extent it does in the processes now used,- or to the extent to be expected from the increased amount of alkali. For instance, garments sent through the usual power laundry fifteen times .usually suffer a twelve to fifteen percent loss of tensile strength.` Similar garments sent through a similary power laundry using the detergent of this invention seem to lose tensile strength at less than onehalf of this rate andin a number of instances have shown only about four percent loss of tensile strength.

In summary, it is asserted that the detergentv of this invention washesfabrics cleaner and more thoroughly than detergents previously used with less injury tothe fabrics and moreover that it reduces the washing time and the consumption of materials, particularly water which is one .of the large elements of expense in power ylaundry practice.

AWhile lt `is posslbIe to adams ingredients to the washing bath or textile treating bath sepa-V rately, it is recommended that for most purposes, particularly for power laundry use, the ingredients be pre-combined and thoroughly admixed. In regard to the power laundry use, for instance, the ingredients when admixed in the appropriate proportions, provide a detergent which can be used in finely divided, powdered or granulated formso that it dissolves readily inthe washer. Mahogany sulphonates and particularly mahogany sulphonates commercially available in this country, are thick, gummy, sticky bodies," very diiiicult to handle, pour, measure or remove from shipping containers. The fatty acid soaps' and mahoganyy sulphonates mixed are a viscous jelllike mass,`diliicult to handle. If, however, two, three, five or more times the amount of dry alkali salt, such as sodium carbonate, be mixed with the mahogany sulphonates and the fatty acid soap, then the detergent becomes a hard, dry

body which can'be reduced to finely divided or 1 powdered form and readily shipped, handled and measured. It is recommended that the alkali be three tove times the weight of the soap. sulphonate admixture.

The proportioning of ingredients to provide the nely divided detergent, as distinguished from a jell-like detergent, is an important element of this invention. The invention and its many specific advantages can be best understood in relation to the following examples of specific uses of the detergent.

Laundry `practice In modern laundry practice the detergents used consist of high titre fatty acid soaps and alkalies. The ratio of soap to alkali `and the type of alkali used varies to some `extent in different -plants and also depending upon the type of soil to be removed. Ordinarily a ratio of one part of soap to one part of an alkali; consisting of sodium carbonate or a mixture of sodium carbonates and bicarbonate or sodium silicate or sodium phosphate, has been :found to give the most satisfactory results.

It` has also been found that a preliminary treatment of cold water and alkali and possibly a small amount of soap, usually termed a break followed by a number of separate sudsing operations produces a greater detergent action for aA given amount ofl fatty soap and alkali than if the same quantity of soap and alkali is used in case of white Work) a sufficient number of rinses to remove the last traces of soaps, a treatment with a mild acid termed the sour to remove the last traces of soaps and alkali and finally a bluing and siZing-operation'to improve the lappearance and finish of the Washed materials.

The use of a number of sudsing operations results in improved quality but only at the expense of time of treatment and quantity of water required.

I, have found that the properties of `a detergent' comprising a Ablend. of fatty acid' soaps and mahogany sulphonates are so different from the or'dinaryfatty acid soaps that an entirely different` washing procedureA whichresults in a material saving in time and water may be employed.

This detergent is also most effective when used with much` greater quantities of alkalies than have been found tobe the most effective with ordinary fatty acid soaps. A. quantity of alkali three to four times greater than that ordinarily used in laundry operations may be used without damage to the material and as a matter of fact on vthe average theloss in tensile strength is less than with the ordinarylaundryprocedure and .tion is required to produce work as clean if not cleaner than that produced by a multiple sudsing treatment with fatty acid soap 'and alkali. The

number and duration of .the rinses may be reduced as the detergent rinses out very easily.

The following example showing the procedure followed in washing a V250 pound load-of house` hold Wash work with the fatty acid sulphonate alkali detergent as compared with fatty 4acid soap and alkali will illustrate the utility and economy of this detergent.

Fatty acid soap sulphonate and Fatty afi? and alkali Wt. of load 250# Break None First suds l0 minutes Second suds- 10 minutes Thirdfmds 10 minutes l0 minutes 10 minutes 10 minutes.l 4-4 mln. rlnses.

-5 min. rinses 5 mln 5 min.

e 5 min. 5 min. Total time 58 minutes 85 minutes Y# fattylaci.. 25# high titre su p oua e. soap Detergent "l 25# soda ash 1 4# soda ash One badly `soiled article was torn in two and half run in each load. At the completion of the washing operation it was found that the piece washed with the fatty acid and sulphonate was 2% whiter than the piece washed with -fatty soap and alkali. l

Silk degummz'ng Raw silk consists .of the true silk or nbroin covered by a coating of silk gum or sericin. The

latter is harsh, non-lustrous and somewhat unstable and must be removed in order that the flbroin may be utilized.\V

Sericin is attacked and rendered partially water soaps area rather expensive source of alkali and recently small amounts of alkali have been added to the degurnming baths in an'eifort to decrease the amount of soap required and to increase the rate of .degumming Extreme care is required in case excess alkali is used as the broin is also attacked by too long an exposure to alkaline solutions or by too high concentrations. d

The minimum soap concentration which has been successfully employed in silk degummingis approximately 1.25% and the maximum excess alkali concentration .03%. Attempts to effect a further reduction in soap concentration or an increase in free alkalinity result either in deposition of sericin in the degumming baths or serious weakening of the silk.

By utilizing an emulsifying and detergent mixture comprising a mixture of from 50 to 85 parts of sodium oleate and 50 to 15 parts of mahogany sulphonate, the concentration of the detergent in the degumming bath may be reduced to as low as .75% and the concentration of the alkali increased to as high as .065% without injury to the silk.

The following examples showing the procedure and concentrations used in degumming with red oil soap and with a blend of red oil soap and sulphonate illustrate the advantages of the fatty soap sulphonate detergent.

Fatty soapsulplionato Fatty Soap Ratio silk to solution l to 50 l to 50. Detergent concentration .75% of 70% red oil 1.25%.

i soap; 30% mahognny sulphonate. Alkali concentration .65 gram NnOlI .3 gram NaOH per liter. per liter. Temperature .Just below boil Justbelowboil. 'Iime 45 minutes 45 minutes. Boil off loss 23 l 23.3.

From the above results it will be seen that the amount of detergent can be reduced by 40% without any increases in time of degumming and without weakening of the silk.

If the concentration of the red oil sulphonate mixture is increased to 1.25% the time may be reduced to 30 minutes, resulting in a saving in time of 331/3 per cent.

Treatment of wool to facilitate the spinning and weavingv operations:

must be removed prior to dyeing which necessitates a second scouring operation. In the fulling operation which is carried out as a part of the nal finishing operation, detergent solutions and alkalies are also used.

-Wool is quite sensitive to the action of alkawhich must be removedl dmately one-third less of .lies and care must bel exercised in using alkalies in the scouring baths. employ moderate temperatures, preferably not 'over`140 F. as higher temperatures cause harshening and deteriorate the fibres.

The amount of soapl and the ratio of soap to alkali used in scouring raw wool `varies widely depending upon the character of the wool and the nature. and amount of impurities associated with it, from .25% to 1.25% soap and from 1.25 to A2.5% of Asoda ash being used. The relatively high soda ash content serves to saponify fatty acids which may be present as constituents of the wool grease.

In scouring woven fabrics for removal of the oils used in manufacture from 1.5 to soap and from .5 to 2.5% of soda ash may be used, the preferred amounts depending upon the quantity of spinning oils present and their content of saponiable constituents.

In fulling approximately the same strength soap solutions are used but the alkali used is generally reduced. Alkali is necessary to exert a softening and' swelling action and to accelerate the shrinkage and felting which occurs during the fulling operation.

If in place of fatty acid soap-a blend of from 50 to 85% of fatty acid soap and from 15 to 50% mahogany sulphonate is used the quantity of alkali used in the baths may begreatly increased without affecting the strength of the wool or harshening it or affecting its dyeing properties.

In scouring raw wool the amount of alkali may be doubled and the amount of detergent decreased, the high vemulsifying power of the fatty soap'sulphonate blend in the presence of an appreciable alkali concentration will exert a wetting'out, cleansing and soil dispersing action even when present in a reduced amount.

In scouring piece-goods, the time of scouring and the quantity of detergent may be decreased if the mineral sulphonate fatty soap blend is used. In case the spinning oils have a high mineral oil content it is preferable to use a higher proportion of mahogany sulphonate inthe detergent blend.

The alkali content ofthe fulling baths--may be increased and the fulling time reduced by increasing the alkali content. In the. presence of the mahogany sulphonate and fatty detergent, the wool is not harshened'and the wetting and penetrating powers of the solution are enhanced.

The following example illustrates the use of the mahoganysulphonate fatty soap blend'as compared to the fatty soaps commonly used in scouring woolen piece-goods.

Fatty soap-sulphonate Fatty soap Ratio wool to solution 1 to6 1 to 6.

. 80%-35 titre 3 oz. per gal. fatty acids. 20% palm andred Detergent-2 oz. per gal mahogany suloil soap, 35

5 oz. per gal phonate. titre.

Soda ash 3 oz. per gal. soda ash. Temperature 120 F 120 F. Time 35 min 45 min. E

l'I'he color, appearance and softness of ythe material scoured with the fatty soap sulphonate mix were equal in all respects to the material scoured with fatty soaps, although the scouring time was reduced approximately 20%, approxithe fatty acid sulphonate mix than fatty soap was used.

Claims directed to silk degumming appear in It is also necessary to' 1. A detergenueomprising, an admixture of i to 60% mahogany sulphonates, 90 to 40% fatty acid soap, both of which are adapted to substantially dissolve in water, and a water soluble 10 alkali one-third to thirty times greater in quantity than the quantity of alkali necessary to neutralize the mahogany sulphonic and fatty acid content of the mixture.

A 2.' A. detergent suitable for laundryuse, comprising, an admi'xture adapted to substantially dissolve in Water, of 10 to 6,0%v mahogany sulphonates, 90 to 40% `fatty acid soap, and a quantity of water soluble alkali between three and flve times as great as the weight of said admixture.

3. A detergent suitable for laundry use, comprising, an admixture adapted to dissolve in water, of y 10 to 60% mahogany sulphonates, 90

to 40% red oil soap, and a quantity of water soluble alkali between three andiive times as great as the weight of said admixture.

4. A detergent suitable for laundry use, comprising, an admixture adapted to dissolve in lWater, of 10 .to 60% mahogany sulphonates, 90

to fatty acid soap, and a quantity of water solu le alkaline salt between three and iye times as great as the Weight of said admixture.

5. The process of washing fabrics, which comprises, agitating the fabrics in an aqueous so lution of mahogany sulphonates, faty acid soap, and a quantity of watersoluble ma erial such as caustic oda adapted to provide an alkaline reaction in said solution, said quantity being onethird to thirty times the quantity of alkali neces- 40 sary to neutralize the mahogany sulphonlc and fatty acid content of said solution.

, phonate.

5. The process of laundering fabrics, which comprises, treating the fabrics to be cleaned in a hot aqueous solution containing a detergent comprised of at least approximately 10% to approximately of mahogany sulphonates, and approximately to approximately 40% of fatty acid soap by weight' and a quantity of` alkali approximately two to ve times greater than the combined weight of the 'soap and sul- '7. The process of laundering fabrics, which comprises, agitating the fabrics to becleaned in a hot aqueous solution of mahogany sulphonates, fatty acid soap, and alkali, in whichv solution the.' mahogany-i sulphonate comprises approximately 10% to v90% of the combined weight of the soap and sulphonate, and in which solution the amount of alkali dissolved, by weight, is approximately two to five times greater than the combined weight of the soap and sulphonate'.

8. The process of laundering fabrics, which comprises, treating the fabrics to bey laundered in an aqueous solution in which'mahogany sulphonates, soap, and alkali are dissolved, the amount of soap present comprising at least approximately 40% of the Weight ofthe soap and suiphonate, and the amount of alkali present comprising one-third to thirty times the quantity required to neutralize the mahogany and fatty acid content in said solution.

9. The process of washing fabrics, which comprises, agitating the fabrics in an aqueous solu- I Ation of mahogany sulphonates, fatty acid soap,

and a quantity of water soluble material, such as caustic soda, adapted to provide a reaction in said solution which is highlyalkaline, said quantity being two to five times the combined Weight of the soap and sulphonates' content of said solution.

, WARREN T. REDDISH. 

